Luminescent device

ABSTRACT

A device for stimulable light emission that includes a fiber mat of nanofibers having an average fiber diameter in a range between 100 and 2000 nm, and includes plural stimulable particles disposed in association with the nanofibers. The stimulable particles produce secondary light emission upon receiving primary light at a wavelength λ. The average fiber diameter is comparable in size to the wavelength λ in order to provide scattering sites within the fiber mat for the primary light. Various methods for making suitable luminescent nanofiber mats include: electrospinning a polymer solution including or not including the stimulable particles and forming from the electrospun solution nanofibers having an average fiber diameter between 100 and 2000 nm. Methods, which electrospin without the stimulable particles, introduce the stimulable particles during electrospinning or after electrospinning to the fibers and therefore to the resultant fiber mat.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to U.S. application Ser. No. 10/819,916,filed on Apr. 8, 2004, entitled “Electrospinning of Polymer NanofibersUsing a Rotating Spray Head,” Attorney Docket No. 241015US-2025-2025-20,the entire contents of which are incorporated herein by reference. Thisapplication is also related to U.S. application Ser. No. 10/819,942,filed on Apr. 8, 2004, entitled “Electrospray/electrospinning Apparatusand Method,” Attorney Docket No. 241013US-2025-2025-20, the entirecontents of which are incorporated herein by reference. This applicationis related to U.S. application Ser. No. 10/819,945, filed Apr. 8, 2004,entitled “Electrospinning in a Controlled Gaseous Environment,” AttorneyDocket No. 245016US-2025-2025-20, the entire contents of which areincorporated herein by reference. This application is related to U.S.Ser. No. 11/130,269, filed May 17, 2005 entitled “Nanofiber Mats andProduction Methods Thereof,” Attorney Docket No. 256964US-2025-2025-20,the entire contents of which are incorporated herein by reference. Thisapplication is related to U.S. application Ser. No. ______, filed on______, entitled “Particle Filter System Incorporating Nanofibers,”Attorney Docket No.-2025-2025-20, the entire contents of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Nanofiber mats and methods for producing nanofiber mats having lightemitting properties, and the application of the nanofiber mats inlighting applications.

2. Description of the Related Art

The choice of general illumination sources for commercial andresidential lighting is generally governed by a balance of energyefficiency and the ability to faithfully produce colors as measured bythe color rendering index (CRI). Existing fluorescent lighting is knownto be economical from an energy consumption point of view. However, manyusers complain that the light produced by the existing fluorescentlighting is of poor spectral quality and produces eye strain and otheradverse health effects. Incandescent light is also widely used and isrecognized as having excellent spectral quality and the ability toaccurately render colors. This high spectral quality is derived from thehot filament, which serves as a blackbody radiator and emits light overmany wavelengths, similar to the sun. However, incandescent lightingsuffers from very low energy efficiency. Thus, there is a long felt needto produce light sources that use less energy and have a lightcomposition similar to the composition of the sun light.

Solid-state lighting (SSL) is an alternative general illumination andlighting technology that promises the energy efficiency of fluorescentlights and the excellent spectral qualities of incandescent lighting.Typically, commercially available SSL technologies consists of a lightemitting diode (LED) surrounded by a phosphor composed of largeparticles usually larger than 2 μm. The light emitted from the LED is ofsufficient energy to cause the phosphor to fluoresce and emit one ormore colors of visible light. The most common example of commercial SSLproducts consists of a blue LED (typically 460 nm) surrounded by ayellow phosphor, such as cerium-doped yttrium aluminum garnet (YAG:Ce),that emits lights in a broad band centered at 550 nm. The combination ofthe yellow light emission from the phosphor and blue light from the LEDproduces a light source that has a generally white appearance.Alternatively, an LED that emits in the ultraviolet (<400 nm) can beused to excite a blend of red, green, and blue phosphors. FIG. 1 is aschematic depiction of the spectrum of light obtained from a solid-statelighting device. While this approach produces white light, it suffersfrom low efficiency and poor spectral quality due to the limited numberof wavelengths.

In addition, while the light intensity from current solid-state lightsis sufficient for applications such as flashlights, it is considered toolow and the emission cone is considered too narrow for use in generalillumination applications such as room lighting. Hence, there is a needfor solid-state light sources that are capable of providing highintensity white light emissions over a large enough area for use ingeneral illumination.

One approach proposed to improve the performance of SSL devices has beento use nanoparticles such as quantum dots as secondary converters toproduce white light. “Quantum Dots Lend New Approach to Solid-StateLighting,” Sandia National Laboratory press release Jul. 24, 2003. Thisapproach incorporates quantum dots into a polymer used to encapsulatethe light emitting diode (LED) and essentially creates athree-dimensional dome of quantum dots around the LED die. While thismethod has been successful in producing white light, thethree-dimensional dome structure places large quantities of quantum dotsin non-optimal positions around the LED and creates potential quantumdot agglomeration issues.

Previously, polymer/quantum dot compound nanofibers have been obtainedfrom electrospinning of the polymer/quantum dot composite solutions, asdisclosed in Schlecht et. al., Chem. Mater. 2005, 17, 809-814. However,the nanofibers produced by Schlecht et al. were on the order of 10-20 nmin diameter, in order to produce quantum confinement effects. The sizerange of the nanoparticles and nanofibers disclosed therein is notadvantageous for conversion of a primary light into secondary lightemission across the white light spectrum.

Lu. et. al., Nanotechnology, 2005, 16, 2233, also reported the making ofAg₂S nanoparticles embedded in polymer fiber matrices byelectrospinning. Once again, the size range of the nanoparticles andnanofibers shown therein is not advantageous for conversion of a primarylight into secondary light emission across the white light spectrum.

SUMMARY OF THE INVENTION

In one embodiment of the present invention, there is provided a devicefor stimulable light emission. The device includes a fiber mat ofnanofibers having an average fiber diameter in a range between 100 and2000 mm, and includes plural luminescent particles disposed inassociation with the nanofibers and configured to produce secondarylight emission upon receiving primary light at a wavelength λ. Theaverage fiber diameter is comparable in size to the wavelength λ inorder to provide scattering sites within the fiber mat for the primarylight.

In one embodiment of the present invention, there is provided a methodfor making luminescent fiber mats. The method electrospins a polymersolution including luminescent particles and forms from the electrospunsolution nanofibers having an average fiber diameter between 100 and2000 nm and including the luminescent particles. The method collects thenanofibers to form a fiber mat.

In one embodiment of the present invention, there is provided a methodfor making luminescent fiber mats. The method electrospins a polymersolution to form nanofibers having an average fiber diameter between 100and 2000 nm. The method coats the nanofibers during the electrospinningwith luminescent particles and collects the nanofibers to form a fibermat.

In one embodiment of the present invention, there is provided a methodfor making luminescent fiber mats. The method electrospins a polymersolution to form nanofibers having an average fiber diameter between 100and 2000 nm. The method collects the nanofibers to form a fiber mat andcoats the fiber mat with luminescent particles.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention and many of the attendantadvantages thereof will be readily obtained as the same becomes betterunderstood by reference to the following detailed description whenconsidered in connection with the accompanying drawings, wherein:

FIG. 1 is a schematic depiction of the spectrum of light obtained from aconventional solid-state lighting device;

FIG. 2A is schematic depicting the disposition of luminescent compoundsinside a volume of a fiber, according to one embodiment of the presentinvention;

FIG. 2B is schematic depicting the disposition of luminescent compoundson or near the surface of a fiber, according to one embodiment of thepresent invention;

FIG. 2C is schematic depicting a fiber mat, according to one embodimentof the present invention, in which the fiber mat in total serves as anoptical scattering center;

FIG. 2D is schematic depicting a fiber mat, according to one embodimentof the present invention, in which the fibers serve as individualscattering centers;

FIG. 2E is schematic depicting a fiber mat, according to one embodimentof the present invention, in which the fibers have a distribution ofdifferent size quantum dots on the fibers;

FIG. 3 is the resultant light spectrum from two samples, a fiber mat incurve “a” and a polymer film in curve “b” containing no nanofibers, eachhaving equal concentrations of quantum dots;

FIG. 4 is a schematic illustration depicting an electrospinningapparatus suitable for deposition of fibers and/or nanofibers of thepresent invention including nanoparticle light emitters;

FIG. 5 is a flow chart illustrating a method for forming a luminescentdevice according to an embodiment of the present invention in whichluminescent particles are included in an electrospray polymer;

FIG. 6A is a schematic of a quantum dot dispersion in a polymer matrixat a concentration where agglomeration is present only at a lowconcentration;

FIG. 6B is a schematic of a quantum dot dispersion in a polymer matrixat a concentration where agglomeration is a factor;

FIG. 7 is a flow chart illustrating a method for forming a luminescentdevice according to an embodiment of the present invention in whichluminescent particles are attached to the electrospun fiber during theelectrospinning process;

FIG. 8 is a flow chart illustrating a method for forming a luminescentdevice according to an embodiment of the present invention in whichluminescent particles are attached to the electrospun fiber after theelectrospinning process;

FIG. 9 is a transmission electron microscopy image of a polymer/QDcomposite nanofiber prepared using the method illustrated in FIG. 8;

FIG. 10 is a schematic depicting according to one embodiment of thepresent invention a configuration in which a light emitting diode (LED)couples light through an encapsulant to the fibers including theluminescent materials; and

FIG. 11 is a schematic depicting according to one embodiment of thepresent invention a configuration in which a light emitting diode (LED)couples light through an encapsulant containing therein fibers includingthe luminescent materials.

FIG. 12 is a spectrum of the light emitted from a nanofiber containingCdSe/ZnS core-shell quantum dots made in accordance with one embodimentof this invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Quantum dots are nanoparticles whose dimensions have an order ofmagnitude equivalent to or smaller than the size of an electron at roomtemperature (deBroglie wavelength). When the size of the quantum dot isroughly the same or smaller than the deBroglie wavelength of anelectron, then a potential well is created that artificially confinesthe electron. The size of this potential well determines the quantizedenergy levels available to the electron, as described in the“particle-in-a-box” solution of basic quantum mechanics. Since theenergy levels determine the fluorescent wavelengths of the quantum dot,merely changing the size of the quantum dot changes, to a firstapproximation, the color at which the quantum dot radiates visiblelight. Thus, the quantum confinement effects of the quantum dotsdirectly influence the light emitted from the respective quantum dot,and a broad spectrum of colors may be achieved by assembling quantumdots of different sizes.

A typical quantum dot includes a nanocrystalline core that may besurrounded by a shell of an inorganic material with a higher band gap.This structure is capped with an external organic layer that ensurescompatibility with various solvents. In this context, the entireassembly (i.e., nanocrystalline core, shell of higher band gap material,and organic capping layer) is referred to collectively as a quantum dot.A representative example of such quantum dots consists of a cadmiumselenide nanocrystalline core surrounded by a zinc sulfide shell andcapped with organic ligands such as trioctylphosphine oxide. Such coreshell structures are sold by Evident Technologies of Troy, NY.

The nanocrystalline core of quantum dots may be fabricated from avariety of materials including but not limited to at least one ofsilicon, germanium, indium phosphide, indium gallium phosphide, indiumphosphide, cadmium sulfide, cadmium selenide, lead sulfide, copperoxide, copper selenide, gallium phosphide, mercury sulfide, mercuryselenide, zirconium oxide, zinc oxide, zinc sulfide, zinc selenide, zincsilicate, titanium sulfide, titanium oxide, and tin oxide, etc. Ofparticular utility to the present invention are quantum dots having acore of at least one of CdSe, InGaP, InP, GaP, and ZnSe. The opticalproperties of quantum dots are produced by this nanocrystalline core.

Quantum dots are commercially available as colloidal dispersions in lowdielectric constant (low-K) organic solvents such as toluene. However,quantum dots experience mutual attraction and can agglomerate, which maydisrupt their quantum behavior and change their performancecharacteristics. For example, agglomeration is known to reduce the lightemission efficiency of quantum dots and is known to cause red-shifts inemission frequency due to energy transfer to larger dots formed as aresult of agglomeration. See J. Rodriguez-Viejo, K. F. Jensen, H.Mattoussi, J. Michel, B. O. Dabbousi and M. G. Bawendi, Applied PhysicsLetters, vol. 70 (1997), no. 16, page 21, the entire contents of whichare incorporated herein by reference. Due to the sensitivity of thehuman eye to slight color variations, particle agglomeration can have asignificant impact on the quality of light from an illumination source.In the extreme, agglomeration can lead to quenching of photoluminescencefrom quantum dots.

Nanofibers are a solid structure that has one dimension (diameter) inthe 10-2000 nm range, and the other dimension (length) can be quite longin the meters range. Nanofibers suitable for the present invention canbe made from a variety of materials, including polymers, ceramics, andglasses, sol gels, polyimides, and blends of materials can also bereadily fabricated. One feature of nanofibers is their small diameterand consequently high surface area. Nanofiber diameters on the order ofvisible light (˜500 nm) or even smaller can be readily produced creatingvery large surface areas.

Referring now to the drawings, wherein like reference numerals designateidentical or corresponding parts throughout the several views, invarious embodiments of the present invention, FIGS. 2A and 2B areschematics depicting a light stimulable fibers (LF) 2 including forexample a luminescent particle 4 (i.e., one of the compounds disclosedbelow) disposed either on the surface or in the bulk of the nanofiber.More specifically, FIG. 2A is schematic depicting the disposition ofluminescent particles 4 (e.g., light stimulable particles such asquantum dot semiconductor materials or nano-phosphors) inside a volumeof a fiber 2, which in FIG. 2A is depicted as a nanofiber. FIG. 2B isschematic depicting the disposition of luminescent particles 4 on ornear the surface of a fiber 2, which in FIG. 2B is also depicted as ananofiber. FIG. 2C is schematic depicting a fiber mat 6, according toone embodiment of the present invention, in which the fiber mat 6 intotal serves as an optical scattering center. In this configuration,according to one embodiment of the present invention, stimulableparticles (while not explicitly shown) are disposed in association withthe nanofibers 2 throughout the fiber mat thickness h. The nanofibers 2cumulatively provide scattering sites for excitation (or primary) light,thereby in one embodiment of the present invention enhancing theprobability of interaction between the pump source light and thestimulable particles 4.

FIG. 2D is schematic depicting a fiber mat 6, according to oneembodiment of the present invention, in which the fibers 2 are shown asindividual scattering centers. The nanofibers 2 individually providescattering sites for excitation (or primary) light, thereby in oneembodiment of the present invention enhancing the probability ofinteraction between the pump source light and the stimulable particles4.

Hence, in various embodiments of the present invention to be explainedin greater detail below, there is provided a device including the fibermats shown for example in FIGS. 2C and 2D for stimulable emission from afiber mat. The fiber mat 6 includes nanofibers having an average fiberdiameter in a range between 100 and 2000 nm, and plural light stimulableparticles disposed in association with the nanofibers. The stimulableparticles 4 can produce secondary light emission upon receiving primarylight at a wavelength λ. The average fiber diameter is comparable insize to the wavelength λ in order to provide scattering sites within thefiber mat for the primary light.

As discussed later in greater detail, the average fiber diameter is in arange between 100 to 2000 nm, or more suitably between 300 nm to 600 nm,or more suitably between 400 nm to 500 nm. The average fiber diameter isin a range of 0.50 to 1.50 of the wavelength λ, or more suitably in arange of 0.9 to 1.10 of the wavelength λ. The wavelength λ is in a rangebetween 100 and 2000 nanometers, or more suitably between 400 and 500nanometers. The fiber mat 6 has a thickness in a range between 0.1 and2,000 microns, or more suitably in a range between 1 to 500 microns.

In various embodiments of the present invention, the stimulableparticles 4 include for example besides or in addition to the quantumdot materials listed above nano-phosphors. Nano-phosphors such as forexample in the list below and others are suitable for the presentinvention. Examples of suitable nanophosphors include, but are notlimited to:

1. Rare-Earth doped metal oxide such as Y₂O₃:Tb, Y₂O₃:Eu³⁺, Lu₂O₃:Eu³⁺,CaTiO₃:Pr³⁺, CaO:Er³⁺, (GdZn)O:Eu³⁺;

-   -   2. Rare-Earth doped yttrium aluminum garnet (YAG) such as        YAG:Ce³⁺;    -   3. Rare-Earth doped zirconium oxide such as ZrO₂:Sm³⁺,        ZrO₂:Er³⁺;    -   4. Rare-Earth doped vanadate (YVO₄:Eu) and phosphate        (La,Ce,Tb)PO₄;    -   5. Doped materials consisting of a host matrix (e.g., Gd₂O₃,        GdO₂S, PbO, ZnO, ZnS, ZnSe) and a dopant (Eu, Tb, Tm and Mn);        and    -   6. Metal-doped forms of zinc sulfide and zinc selenide (e.g.,        ZnS:Mn²⁺, ZnS:Cu⁺).

Of particular utility to the present invention are nanonphosphorsincluding at least one of rare-Earth doped YAG, doped ZnS, and dopedZnSe.

Further, as discussed in more detail later, the stimulable particles 4can include a plurality of color-distinctive light emitters (i.e., adistribution of different sized quantum dots or a distribution ofnano-phosphors) which produce respective secondary light emissions fromthe primary light and thereby form a resultant white light having acolor rendering index greater than 70, or greater than 80. FIG. 2E isschematic depicting a fiber mat 6, according to one embodiment of thepresent invention, in which the fibers have a distribution of differentsize quantum dots on the fibers.

In one embodiment of the present invention, by dispersing the stimulableparticles 4 on a high surface area medium such as for example a fibermat of nanofibers, the emission efficiency of a fiber mat 6 containingthe nanofibers 2 and the stimulable particles 4 (e.g., the quantum dots)is increased above that achieved with planar packing of the luminescentparticles are dispersed in a film. As a result, in one embodiment of thepresent invention, such a nanofiber mat structure can capture, with ahigher efficiency than if the quantum dots were dispersed in a film,photons emitted by an LED and re-radiate at visible wavelengths withhigher intensities than would be possible with planar packed luminescentparticles.

While not limited to any particular theory, light scattered from thefibers 2 depends on the fiber diameter, light wavelength, orientation ofthe fiber to the light and the refractive index of the fibers. Polymersof the fibers have real refractive indices in the range between 1.3 to1.6. Examples of the light scattering efficiency curves for long fibersof slightly absorbing materials (and which may act in a similar manneras the nanofiber structures of the present invention) have been detailedpreviously by Van de Hulst, in Light Scattering by Small particles,Dover, 1957. In that earlier work, for an incident light of 300 nm, themaximum light scattering has a size parameter (π times fiberdiameter/wavelength) of 3.14 and a scattering efficiency (Q) of Q₁=4.2.For incident light at 600 nm, the size parameter is 1.6 and Q₁=2.Therefore, the shorter wavelength light (expected to be used frequentlyin the present invention) is twice as likely of being trapped in the matof fibers than the longer wavelength light. An alternative explanationof this phenomenon is that, on average, the optical path length (OPL) oflight at 400 nm through an appropriately designed nanofiber material islonger than the OPL of 600 nm light. The implications of this phenomenaas applied to the present invention are that an enhancement of lightemission may be obtained from the light scattering characteristics ofthe fibers in the fiber mat (i.e., each fiber acting as a scatteringcenter, and the mat of fibers acting as a medium to more effectivelyconfine the excitation light in the fiber mat medium permitting a higherprobability that the excitation light would interact with a lightemitter during its residence in the fiber mat.

For example, in the present invention a typical excitation frequency isblue light at 450 nm. In order to produce white light, the structurewill need to emit radiation over a broad range of frequencies from 450nm to 800 nm. By fabricating a nanofiber structure in which the averagediameter of the nanofibers 4 in the mat 6 is roughly the same as that ofthe excitation source (i.e., 450 nm), the excitation frequency can beeffectively trapped in the nanofiber structure by light scattering(i.e., OPL of the excitation source is long). This increases thelikelihood that the excitation source will initiate fluorescence andproduce white light. In contrast, the longer wavelength emissionsproduced by fluorescence of the luminescent compound will be scatteredless effectively by the nanofibers in the fiber mat, and are more likelyto emerge from the fiber mat structure with minimal scattering. Underthese conditions, the light scattering/photonic properties as a functionof wavelength and fiber diameter are improved.

In one embodiment of the present invention, the fiber mat 6 includes anumber of nanofibers layers (as shown in FIG. 2C). The nanofibers 2 ofthese layers serve individually as scattering centers for the incidentexcitation light. Typically, the nanofibers have an average diameterthat is approximately that of the wavelength of the excitation source(i.e., from 200-500 nm). Furthermore, the number of layers in the fibermay typically form a thickness for the fiber mat 6 in a range of 0.1 to2,000 microns, although thinner values such as for example 0.01 micronsand thicker values such as for example 3,000 microns are suitable. Thethinner layers may not be as likely to “capture” the incident excitationlight, and the thicker layers may substantially scatter the inducedlight from the quantum dots.

To verify the effect of appropriately sized fibers in a light stimulablestructure of the present invention (i.e., fibers sized to a diameterthat is close to the excitation frequency wavelength), a fiber mathaving nanofibers with an average diameter of 450 nm and a polymer filmcontaining no nanofibers were prepared. Both materials had equal amountsof quantum dots (i.e., luminescent compounds).

FIG. 3 is the resultant light spectrum from these two samples. When thequantum dots are dispersed in the nanofibers, the intensity offluorescent emission increased by roughly an order-of-magnitude ascompared to the polymer film sample, as indicated by the intensity oflight emissions of the 540 nm peak in the corresponding spectrum shownby curve “a” in contrast to curve “b” of the polymer film sample. Thisimprovement in performance is believed to be due to the difference instructure between a nanofiber matrix and the solid film, as explainedabove. That is, the nanofiber mat of the present invention permitshigher energy light (e.g., UV excitation) to be more efficientlycaptured by the quantum dots to produce higher intensity light emissionfrom the quantum dot containing medium. It is likely that agglomerationdid not reduce intensity in the solid film because there is little redshift seen in the spectra for the solid film (i.e., curve “b”).Moreover, using transmission electron microscopy (TEM) andUltraViolet-Visible Spectroscopy, the quantum dots were found to beuniformly dispersed throughout the fiber mat, regardless of size.

Fabrication Procedures

Formation of the light stimulable structures in the present inventioncan occur through a number of methods. The formation methods typicallyinvolve the formation of nanofibers 2 of a controlled diameter and theapplication of the stimulable particles 4 (e.g., quantum dots) to thenanofibers 2. In one method, stimulable particles 4 can be applied tothe electrospun fibers as the fibers are coalescing into a resultantfiber mat. In one method, stimulable particles 4 can be included in theelectrospray medium. In one method, stimulable particles 4 can beapplied to the resultant fiber mat after the mat has been formed withoutany stimulable particles.

FIG. 4 is a schematic illustration depicting an electrospinningapparatus suitable for deposition of fibers and/or nanofibers of thepresent invention, including the deposition of fibers and/or nanofibershaving stimulable particles 4 including nanoparticle light emitters suchas the above-noted quantum dots and nano-phosphors. In one embodiment ofthe present invention, the stimulable particles 4 incorporated into thefibers and/or nanofibers of the present invention are smaller than thediameter of the nanofibers.

In FIG. 4, an electrospinning apparatus 21 includes a chamber 22surrounding an electrospinning element 24. As such, the electrospinningelement 24 is configured to electrospin a substance from which fibersare composed to form fibers 26. The electrospinning apparatus 21includes a collector 28 disposed from the electrospinning element 24 andconfigured to collect the fibers and/or nanofibers. Various methods forforming fibers and nanofibers are described in U.S. Ser. Nos.10/819,942, 10/819,945, and 10/819,916 listed and incorporated byreference above.

The electrospinning element 24 communicates with a reservoir supply 30containing the electrospray medium such as for example the above-notedpolymer solution. The electrospray medium of the present inventionincludes polymer solutions and/or melts known in the art for theextrusion of fibers including extrusions of nanofiber materials. Indeed,polymers and solvents suitable for the present invention include forexample polystyrene in dimethylformamide or toluene, polycaprolactone indimethylformamide/methylene chloride mixture, poly(ethyleneoxide) indistilled water, poly(acrylic acid) in distilled water, poly(methylmethacrylate) PMMA in acetone, cellulose acetate in acetone,polyacrylonitrile in dimethylformamide, polylactide in dichloromethaneor dimethylformamide, and poly(vinylalcohol) in distilled water andcombinations thereof. In general, suitable solvents for the presentinvention include both organic and inorganic solvents in which polymerscan be dissolved. The polymer materials when formed are preferablytransparent materials, although the polymers may be spun with additivesthat act as color filters for the luminescent compounds (as discussed inmore detail later).

A high voltage source 34 is provided to maintain the electrospinningelement 24 at a high voltage. The collector 28 is placed preferably 1 to100 cm away from the tip of the electrospinning element 24. Thecollector 28 can be a plate or a screen. Typically, an electric fieldstrength between 2,000 and 400,000 V/m is established by the highvoltage source 34. Typically, the collector 28 is grounded, and thefibers 26 produced by electrospinning from the electrospinning elements24 are directed by the electric field 32 toward the collector 28. Theelectric field 32 pulls the substance from which the fiber is to becomposed as a filament or liquid jet 42 of fluid from the tip of theelectrospinning element 24. A supply of the substance to eachelectrospinning element 24 is preferably balanced with the electricfield strength responsible for extracting the substance from which thefibers are to be composed so that a droplet shape exiting theelectrospinning element 24 is maintained constant. In the polymersolutions (or alternatively introduced onto the fibers after or duringthe electrospinning process) are luminescent compounds. The fibersdeposited in the one embodiment of the present invention may range from50 nm to several microns in diameter.

As in the related application, U.S. Ser. No. 11/130,269, previouslyincorporated by reference, the present invention can use differentelectrospinning elements to generate a fiber mat of mixed fibers ofdifferent sized fibers. The fiber mat can have for example one side ofthe mat with a larger average fiber diameter than another side of thefiber mat.

The fibers used in the nanofibers of the present invention include, butare not limited to, acrylonitrile/butadiene copolymer, cellulose,cellulose acetate, chitosan, collagen, DNA, fibrinogen, fibronectin,nylon, poly(acrylic acid), poly(chloro styrene), poly(dimethylsiloxane), poly(ether imide), poly(ether sulfone), poly(ethyl acrylate),poly(ethyl vinyl acetate), poly(ethyl-co-vinyl acetate), poly(ethyleneoxide), poly(ethylene terephthalate), poly(lactic acid-co-glycolicacid), poly(methacrylic acid) salt, poly(methyl methacrylate),poly(methyl styrene), poly(styrene sulfonic acid) salt, poly(styrenesulfonyl fluoride), poly(styrene-co-acrylonitrile),poly(styrene-co-butadiene), poly(styrene-co-divinyl benzene), poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidenefluoride), polyacrylamide, polyacrylonitrile, polyamide, polyaniline,polybenzimidazole, polycaprolactone, polycarbonate,poly(dimethylsiloxane-co-polyethyleneoxide), poly(etheretherketone),polyethylene, polyethyleneimine, polyimide, polyisoprene, polylactide,polypropylene, polystyrene, polysulfone, polyurethane,poly(vinylpyrrolidone), proteins, SEBS copolymer, silk, andstyrene/isoprene copolymer.

Additionally, nanofibers containing polymer blends can also be producedas long as the two or more polymers are soluble in a common solvent. Afew examples would be: poly(vinylidene fluoride)-blend-poly(methylmethacrylate), polystyrene-blend-poly(vinylmethylether), poly(methylmethacrylate)-blend-poly(ethyleneoxide), poly(hydroxypropylmethacrylate)-blend poly(vinylpyrrolidone),poly(hydroxybutyrate)-blend-poly(ethylene oxide), proteinblend-polyethyleneoxide, polylactide-blend-polyvinylpyrrolidone,polystyrene-blend-polyester, polyester-blend-poly(hyroxyethylmethacrylate), poly(ethylene oxide)-blend poly(methyl methacrylate),poly(hydroxystyrene)-blend-poly(ethylene oxide)).

Light Emitter Embedment

In general, FIG. 5 is a flow chart illustrating the first above-notedmethod for forming a luminescent device according to an embodiment ofthe present invention in which stimulable particles 4 are included in anelectrospun polymer. At 500, a polymer solution including stimulableparticles (e.g., light stimulable particles) is electrospun usingconditions described above. At 510, from the electrospun solution,nanofibers are formed having a diameter between 100 and 2000 nm andincluding the stimulable particles. At 520, the nanofibers are collectedto form a fiber mat.

The process at 500 reflects the general techniques described above forelectrospraying nanofibers preferably under controlled conditions. At500, care is taken to sonicate the stimulable compounds in solvent priorto mixing with the polymer in the reservoir 30 to ensure adequatedispersion. Adequate dispersion results in a uniform distribution of thestimulable particles throughout the resultant fiber mat. Normally, asonication time greater than 24 hours is sufficient to obtain a uniformluminescent compound suspension in the solution. The ratio of polymer toluminescent compound in the solution will typically range from 2:1 to100:1

Further, according to one embodiment of the present invention, a localconcentration of the stimulable particles in the polymer solution thatis too high can result in deleterious agglomeration of these compounds.FIG. 6A is a schematic of a stimulable particle 4 (i.e., quantum dot,luminescent or light stimulable compound) dispersion in a polymer matrix10 at a concentration where agglomeration is at a low concentration, andtypically is not a factor. FIG. 6B is a schematic of a quantum dot 4dispersion in a polymer matrix 10 at a concentration where agglomerationis a factor. Agglomeration can become an issue even at lowconcentrations, since small particles often experience electrostaticattraction. However, the present invention utilizes the high surfacearea nanofibers to reduce particle agglomeration presumable due to theability of the high surface area nanofiber to accommodate large amountsof nanoparticles.

In one embodiment of the present invention, agglomeration is undesirablesince it results in non-uniformity in the dispersion of the luminescentcompound in the resultant fibers. Agglomeration can change the coloruniformity of the resultant light emissions. In addition, agglomerationalso degrades the optical properties of the luminescent compound bycausing a red-shifting of the emission frequency and a reduction ofemission intensity due to quenching.

The size distribution of the nanoparticles can be controlled by managinga number of parameters such as for example: changing an organic phase ofa solvent system, changing a temperature at which the nanoparticles areformed, alternating reactant concentrations used to form thenanoparticles, changing the capping molecule chemistry, addingsurfactants to control a coagulation of the material from which thenanoparticles are to be formed, applying an electrical or magnetic fieldduring particle nucleation, applying acoustical energy during theformation of the nanoparticles, etc.

The capping molecule chemistry can include for example forming a shellaround the nanoparticle (i.e., the quantum dot) to chemically stabilizethe nanoparticle. The surfactants (e.g., organic ligands) can beincluded around and attached to the outside of the shells to promotesolution and prevent agglomeration. Such surfactants help preventagglomeration of nanoparticles when the nanoparticles are created orused in a dry state. Alternatively, a separation method such aselectrophoretic separation can be used after the particle nucleation toachieve a desired particle distribution.

At 500, the electrospinning solution can include additives such as forexample organic luminescent materials (dye), ceramics, organo-metallic,carbon, and or metal. For example, the index of refraction of thenanofibers can be increased by adding a material with a high dielectricconstant, such as a ceramic like TiO₂. The additives are incorporatedinto a polymer to impart desired physical, chemical, or mechanicalproperties. The additives are usually mixed with the polymer prior toelectrospinning and do not generally form strong chemical bonds with thepolymer. Examples of common additives found in polymers suitable for thepresent invention include pigments (e.g., titanium dioxide), conductivematerials (e.g., carbon or metallic flakes), UV stabilizers, and glassreinforcements.

At 510, the conditions in the electrospinning environment arecontrolled. U.S. Ser. No. 10/819,945 entitled “Electrospinning in aControlled Gaseous Environment” describes techniques applicable to thepresent invention for controlling the electrospraying environment.Additionally, refinements of the electrospinning process are describedin U.S. application Ser. No. ______, entitled “Filter IncorporatingNanofibers,” previously incorporated herein by reference. The practicesdescribed therein can be used in the present invention to produce smalldiameter nanofibers whose large surface to volume ratio can enhance thebrightness of the light emitted from the resultant fiber mat and whoseaverage fiber diameter size is appropriately sized to match the incidentlight source wavelength.

At 520, techniques in U.S. application Ser. No. 10/819,916, entitled“Electrospinning of Fibers using a Rotatable Spray Head” to obtainaligned fibers or techniques in U.S. application Ser. No. 10/819,916,entitled “Filter Incorporating Nanofibers” can be used to improve fibermat density and uniformity.

Light Emitter Incorporation onto Nanofibers During Electrospinning

In one embodiment of the present invention, as discussed above,stimulable particles 4 can be applied to the electrospun fibers 2 as thefibers are coalescing into a resultant fiber mat 6. FIG. 7 is a flowchart illustrating a method for forming a luminescent device accordingto an embodiment of the present invention in which stimulable particles4 are attached to the electrospun fiber during the electrospinningprocess. At 700, a polymer solution is electrospun to form nanofibershaving a diameter between 100 and 2000 nm. At 710, the nanofibers arecoated during the electrospinning with stimulable particles 4. At 720,the nanofibers are collected to form a fiber mat 6.

In this embodiment, the stimulable particles 4 become positioned at ornear the surface of the nanofiber as shown in FIG. 2B. The process at700 is similar to the process at 500 reflecting the general techniquesdescribed above for electrospraying nanofibers in one embodiment undercontrolled conditions. At 710, stimulable particles 4 are attached ontoa surface of the electrospun fibers before the electrospun fibers havedried. At 710, the stimulable particles 4 can be introduced by anelectrospray beam directed to a position removed from an electrosprayingtip electrospinning the polymer solution. FIG. 4 shows an electrosprayunit 48 for introducing the stimulable particles 4 into theelectrospinning environment 46.

Low agglomeration of stimulable particles 4 can be achieved byseparating the nanofiber formation and light stimulable particleattachment steps. This can be achieved in one embodiment of the presentinvention by introducing for example stimulable particles 4 (such asfrom an electrospray solution) into a region where an emerging nanofiberis drying. In an electrospray introduction technique, submicron dropletsof the stimulable particle suspensions are generated byelectrostatically disrupting a droplet of a solvent (such as for exampletoluene) containing the quantum dots. The electrosprayed droplets arehighly charged (usually positively charged) and do not aggregate due torepulsion of similar charges during their passage to the surface of thepolymer nanofiber 6 that, in one embodiment, can be carrying an opposingelectrical charge.

Since the nanofiber is drying during ejection from the needle, in oneembodiment of the present invention, the location of the electrospraycontrols the penetration of the stimulable particles 4 into thenanofiber 2. For example, if the electrospray beam is moved closely tothe electrospraying tip, the nanofibers will likely be softer since theywill contain more solvent and the stimulable particles 4 will embeddeeper into the fiber. Alternatively, if the electrospray beam is movedaway from the electrospraying tip and closer to the collector, thenanofibers will be drier and the stimulable particles will be restrictedto the surface. Other parameters such as the solvent used to dispersethe stimulable particles may also influence the penetration depth of theelectrosprayed quantum dots.

At 710, the processes described in U.S. Ser. No. 10/819,945 entitled“Electrospinning in a Controlled Gaseous Environment” for controllingthe electrospraying environment to influence (retard) the drying rate ofthe electrospun fibers are applicable. At 710, the processes describedin U.S. Ser. No. 11/130,269 entitled “Nanofiber Mats and ProductionMethods Thereof” with regard to the delivery and incorporation ofparticles into fibers are applicable to the present invention.

The process at 720 is similar to the processes described above at 520.

Light Emitter Incorporation onto Nanofibers after Electrospinning

In one embodiment of the present invention, as discussed above, lightstimulable particles such as for example quantum dots can be applied tothe fiber mats after electrospinning. This embodiment is illustrated inFIG. 8. According to this embodiment of the present invention, a fibermat is formed in 800 by electrospinning methods such as for example thetechniques described above. At 810, a solution containing the stimulableparticles 4 is provided (such as the polymer solution in FIG. 6A). At820, the nanofiber mat 6 is immersed into the solution. The solution isselected such that the fiber mat does not dissolve but slightly swellthe polymers existing in the fiber mat 6.

During the embedment process, the polymer nanofibers may swell due tothe solvent. This expansion of the fibers in the network also expandsthe spaces between the fibers, thus opening the network spaces to allowthe particles to move in between. Thus, the particles move to the fibersurface due to the Brownian motion. The fiber mat 6 may be immersed inthe solution for a period of 1 minute to 72 hours and may be rinsed witha solvent for 20-60 seconds to ensure the removal of any looselyattached surface particles. The fiber mat 6 may then be placed onto asupport and allowed to completely dry under room temperature before use.

FIG. 9 is a transmission electron microscopy image of a polymer/quantumdot composite nanofiber prepared using the method illustrated in FIG. 8.Individual quantum dots 4 are visible at both outside and inside of thefiber 2 in the transmission electron microscopic image of a decoratedfiber as shown in FIG. 9. The size of the quantum dots indicates almostno aggregation of the dots.

The surface density of the light stimulable particles on the polymernanofibers made according to the method of the present inventiondescribed in FIG. 8 is controllable by changing variables such as theimmersion time of the fibers, nanoparticle solution concentration, thesolvent composition, and temperature. The factors such as highertemperature that increase Brownian motion and softens the nanofibermatrix (trace solvents mixed with the non-solvent used in the process)may control both the surface coverage as well as the degree of embedmentof the nanoparticles on the fiber. Based on microscopy and the mechanicsof the process, the quantum dots (or nanoparticles) embedment may belocalized in the periphery of the nanofibers.

While nanoparticle incorporation into a matrix such as a fiber or fibermat is described in the present invention, this aspect of the presentinvention is not so limited to electrospinning and fibers. A variety ofprocesses, including the above-noted electrospinning, and otherconventional techniques such as spin coating, aerosol handling,electrostatic method, extrusion of filled polymers, self-assemblednanolayers, etc. can be used according to the present invention to forma matrix having a predetermined distribution of luminescent or lightstimulable compounds. In those examples, the matrix need not beelctrospun fibers and provides a host upon which exposure to a solventof the matrix (with the solvent containing a dispersion of thenanoparticles) will result in the embedment of the nanoparticle (i.e.,quantum dots, nononphosphors, or electroluminescent particles) into thematrix. The matrix material is preferably organic-based but couldinclude sol-gel materials containing inorganic bases.

Relative Light Emitter Distribution

In one embodiment of the present invention, the luminescent compoundsused to make the light stimulable devices of the present invention arenanoparticles forming for example either quantum dots or nano-phosphors.Quantum dots (i.e., the stimulable particles 4) emit electromagneticwaves at wavelengths that depend, to a first approximation, on thediameter of the nanoparticles. For example, CdSe nanoparticles of 2.8 nmnominal diameter emit green light at roughly 530 nm, whereas CdSenanoparticles of 5.0 nm nominal diameter emit red light at roughly 625nm. An emission spectrum from such a sample is shown in FIG. 12. Themixing of specific nanoparticles (each having a characteristicwavelength emission) can be used in the present invention to produce“white light” similar to the mixing techniques used in the mixing ofphosphors for fluorescent lights.

In one embodiment of the present invention, the nominal sizes disclosedfor the stimulable particles can have a variance in size distribution orsurface structure that results in broad-band (as compared to discrete orline emissions). For example, quantum dots of a narrow size distributionthat do not contain an inorganic shell layer may exhibit broadbandemission due to excitation of surface defects and traps. An example ofsuch materials is found in Bowers et al Journal of the American ChemicalSociety vol. 127 (2005) pages 15378-15379 the entire contents of whichare incorporated here by reference. Likewise, broad size distributionsof core shell quantum dots can be produced by controlling the parametersof the reaction used to synthesize them. The broad band emissionsemulate black body radiation sources. Luminescent devices of the presentinvention exhibiting broad band emissions have a higher color renderingindex.

In one embodiment of the present invention, because nanoparticles emitlight having a wavelength depending on the diameter of thenanoparticles, white light may be generated from a fiber mat havingdifferent diameter nanoparticles dispersed throughout. For example,nanoparticles having a first diameter may produce an electromagneticwave having a first wavelength, nanoparticles having a second diametermay produce an electromagnetic wave having a second wavelength, and soon until the plurality of nanoparticles produce all the wavelengthsnecessary to produce a desired spectrum such as that of a blackbodyradiator having a CRI approaching 100.

Below are examples of such mixtures determined with regard to variousexcitation sources:

EXAMPLE 1 Excitation Source: Blue LED at 450-460 nm

Luminescent compound: a single variety of CdSe/ZnS core shell quantumdots with particle diameter 2.6-3.2 nm (configured for yellow emissionand commercially available from Evident Technologies)

Such yellow emitting quantum dots in this example are incorporated intoand onto the fibers at weight percentages between 0.1% and 30% (weightquantum dots/weight fiber) with a more suitable range of weightpercentage between 1% and 10% depending upon desired light output.

When packaged with the blue LED emitting at 450-460 nm, the blue lightfrom the LED and the yellow emission from the photoluminescent fiber inthis example blend to produce white light.

EXAMPLE 2 Excitation Source: Blue LED at 450-460 nm

Luminescent compound: Two different sizes of CdSe/ZnSe core shellquantum dots with the particle diameter of the first size being 2.4 nm(green emission) and the particle diameter of second size being 5.2 nm(red emission) (purchased from Evident Technologies).

These two sizes of luminescent quantum dots are incorporated into andonto the fibers at weight percentages between 0.1% and 30% (total weightquantum dots/weight fiber) with a more suitable range of weightpercentage between 1% and 10%. The ratio of green particles to redparticles incorporated into and on the fibers varies between 0.5:1 to4:1 depending upon desired light output.

When packaged with a blue LED emitting at 450-460 nm, the blue lightfrom the LED and the green and yellow emission from the photoluminescentfiber in this example blend to produce white light.

EXAMPLE 3 Excitation Source: Violet LED at 408 mm

Luminescent compound: Two different sizes of CdSe/ZnSe core shellquantum dots with the particle diameter of the first size being 2.4 nm(green emission) and the particle diameter of the second size being 5.2nm (red emission) purchased from Evident Technologies).

These two sizes of luminescent quantum dots are incorporated into andonto the fibers at weight percentages between 0.1% and 30% (total weightquantum dots/weight fiber) with a more suitable range of weightpercentage between 1% and 10%. The ratio of green particles to redparticles incorporated into and on the fibers varies between 0.5:1 to5:1 depending upon desired light output.

When packaged with a violet emitting LED at 408 nm, white light isproduced in this example by blending the emission of red and greencolors by the photoluminescent nanofiber combined with the violetemission of the LED.

EXAMPLE 4 Excitation Source: Violet LED at 408 nm

Luminescent compound: Three different sizes of CdSe/ZnSe core shellquantum dots with the particle diameter of the first size being 1.9 nm(blue emission), the particle diameter of the second size being 2.4 nm(green emission), and the particle diameter of third size being 5.2 nm(red emission) (purchased from Evident Technologies).

These three sizes of luminescent quantum dots are incorporated into andonto the fibers at weight percentages between 0.1% and 30% (total weightquantum dots/weight fiber) with a more suitable range of weightpercentage between 1% and 10%. The ratio of blue particles to greenparticles to red particles incorporated into and on the fibers variesbetween 1:1:0.5 to 5:5:4 depending upon desired light output.

When packaged with a violet emitting LED at 408 nm, white light isproduced in this example by blending the emission of blue, red, andgreen colors by the photoluminescent nanofiber. Little to no visibleradiation from the LED contributes directly to the white light product.

EXAMPLE 5 Excitation Source: UV LED at 350-370 nm

Luminescent compound: Three different sizes of CdSe/ZnSe core shellquantum dots with the particle diameter of the first size being 1.9 nm(blue emission), the particle diameter of the second size being 2.4 mm(green emission), and the particle diameter of third size being 5.2 nm(red emission) (purchased from Evident Technologies).

These three sizes of luminescent quantum dots are incorporated into andonto the fibers at weight percentages between 0.1% and 30% (total weightquantum dots/weight fiber) with a more suitable range of weightpercentage between 1% and 10%. The ratio of blue particles to greenparticles to red particles incorporated into and on the fibers variesbetween 1:1:0.5 to 5:5:1 depending upon desired light output.

When packaged with a UV emitting LED at 350-370 nm, white light isproduced by the blending of emissions of the blue, red, and green colorsby the photoluminescent nanofiber.

EXAMPLE 6 Excitation Source: Violet LED at 408 nm

Luminescent compound: White-light producing CdSe nanocrystals asdescribed by Bowers et al, in White-light Emission from Magic SizedCadmium Selenide Nanocrystals, J, American Chemical Society 2005, 127,15378-15379. These nanocrystals emit broad band radiation that to theeye appears white due to charge recombination from surface states.

These nanocrystals are incorporated into and onto the fibers at weightpercentages between 0.1% and 30% (total weight quantum dots/weightfiber) with a more suitable range of weight percentage between 1% and10%.

When packaged with a violet emitting LED at 408 nm, white light isproduced in this example. Little to no visible radiation from the LEDcontributes to the white light product.

EXAMPLE 7 Excitation Source: UV LED at 350-370 nm

Luminescent compound: Three different sizes of CdSe/ZnSe core shellquantum dots with the particle diameter of the first size being 1.9 nm(blue emission), the particle diameter of the second size being 2.4 nm(green emission), and the particle diameter of third size being 5.2 nm(red emission) (purchased from Evident Technologies).

The particles are incorporated into the nanofiber in different methods.For example, the red and green quantum dots, which can absorb bluelight, can be placed in the interior of the nanofiber by pre-mixing thered and green quantum dots with the polymer solution used forelectrospinning (Embodiment I). Then the blue quantum dots can be addedto the surface of the nanofiber using either the electrospray(Embodiment II) or liquid-phase coating (Embodiment III) methodsdescribed above. The three sizes of luminescent quantum dots areincorporated into and onto the fibers at weight percentages between 0.1%and 30% (total weight quantum dots/weight fiber) with a more suitablerange of weight percentage between 1% and 10%. The ratio of blueparticles to green particles to red particles incorporated into and onthe fibers varies between 1:1:0.5 to 5:5:1 depending upon desired lightoutput.

When packaged with a UV emitting LED at 350-370 nm, white light isproduced by the blending of emissions of the blue, red, and green colorsby the photoluminescent

Luminescent Devices

In one embodiment of the present invention, an electrospun fiber matincluding luminescent materials is included in an encapsulant such asfor example an epoxy matrix. FIG. 10 is a schematic depicting accordingto one embodiment of the present invention a configuration in which alight emitting diode (LED) couples light through an encapsulant to thefibers including the luminescent or light stimulable particles. Morespecifically, FIG. 11 shows LED 50 emitting UV or blue light through ananofiber materials 2, 4 having a certain distribution of quantum dots(not shown). The UV or blue light emitted by LED 50 constitutes theincident light for the nanofiber materials 2, 4. The stimulableparticles 4 (e.g., the quantum dots) absorb the incident light, anddepending on their properties, emit white light. The fiber mat materials2, 4 are encapsulated, for example, in an epoxy encapsulant 52. Theepoxy 52 may encapsulate both the LED 50 and the fiber mat materials 2,4, either completely or partially. The fiber mat materials 2, 4 mayinclude quantum dots of sizes varying from approximately 1.5 nm to 10 nmto produce a light emission across the desired portion of the visiblespectrum. The concentration of various quantum dots (and/or sizedistribution) is controlled, in one embodiment of the present invention,to provide high quality white light similar to solar emissions.

In other examples, a higher concentration of red emitters than blueemitters may be chosen for other non-white light applications. Thus, thepresent invention permits both monochromatic and color-distinctiveluminescent structures to be made by the respective placement of theappropriate quantum dot light emitter in respective areas of theluminescent structure. Prefabricated fiber mats of respective emissioncolors (i.e., white, red, blue, green, or a color combination) can becut and placed in the respective areas, such that a common light sourcecoupled for example through a fiber optic cable would produce differentlight from the respective areas.

According to another embodiment of the present invention, the mat may bedirectly placed on the surface of the LED 50 before the encapsulationwith epoxy. This placement may reduce energy losses from absorption ofUV in the epoxy. Stimulable particles 4 such as the quantum dots may beconcentrated near the LED for a maximum absorbing effect. Further aspart of the bonding of the nanofiber mat to the LED, interstices in thefibers may be filled with a low refractive index polymer, such assilicone, to optimize the scattering effects required to trap the UVlight.

FIG. 10 is a schematic depicting according to one embodiment of thepresent invention a configuration in which a light emitting diode (LED)50 couples light through an encapsulant 52 containing therein fibers 2including the stimulable particles 4. In this embodiment, as shown inFIG. 10, the nanofiber mat including the stimulable particles 4 has beendivided (e.g. chopped) and added as filler to the epoxy encapsulant 52,for example an encapsulant typically used in LEDs. An alternativeapproach is to disperse the fibers by shear of the epoxy. Because thenanofibers may be made small to not interfere with the visible lighttransparency of the clear epoxy, the optical properties of the epoxyshould be unaffected.

Some advantages of the various embodiments of the present invention ascompared to the traditional technology include: 1) providing aluminescent material with broad spectral emission can be created byincorporating a distribution of nanoparticles into the light stimulabledevices of the present invention; 2) creating such a structure requiresless solvent than the casting or electrophoretic methods currently inuse for phosphors; 3) allows emission, transmission, and scatteringproperties of the luminescent material to be controlled separatelythrough a choice of the nanoparticle (i.e., particle density, size,composition, etc.) and nanofiber geometry (i.e., length, diameter,etc.); 4) allows for more efficient operation of the photoluminescentconverter due to higher surface area and control of the fiber geometry;and 5) provides a more convenient process to handle and processnanoparticles in finished devices than alternative approaches.

Numerous modifications and variations of the present invention arepossible in light of the above teachings. It is therefore to beunderstood that within the scope of the appended claims, the inventionmay be practiced otherwise than as specifically described herein.

1. A device for stimulable light emission, comprising: a fiber matincluding, nanofibers having an average fiber diameter in a rangebetween 100 and 2000 nm, and plural light stimulable particles disposedin association with the nanofibers and configured to produce secondarylight emission upon receiving primary light at a wavelength λ; and saidaverage fiber diameter being comparable in size to the wavelength λ inorder to provide scattering sites within the fiber mat for the primarylight.
 2. The device of claim 1, wherein the average fiber diameter isin a range between 300 to 600 nm.
 3. The device of claim 2, wherein theaverage fiber diameter is in a range between 400 nm to 500 nm.
 4. Thedevice of claim 1, wherein the average fiber diameter is in a range of0.50 to 1.50 of the wavelength λ.
 5. The device of claim 4, wherein theaverage fiber diameter is in a range of 0.9 to 1.10 of the wavelength λ.6. The device of claim 1, wherein the wavelength λ is in a range between300 and 600 nanometers.
 7. The device of claim 6, wherein the wavelengthλ is in a range between 400 and 500 nanometers.
 8. The device of claim1, wherein the fiber mat has a thickness in a range between 0.01 micronsand 2,000 microns.
 9. The device of claim 1, wherein the fiber mat has athickness in a range between 1 to 500 microns.
 10. The device of claim1, wherein the stimulable particles comprise luminescent particles. 11.The device of claim 10, wherein the luminescent particles comprise atleast one of quantum dots and nano-phosphors.
 12. The device of claim11, wherein the quantum dots comprise at least one of silicon,germanium, indium phosphide, indium gallium phosphide, indium phosphide,cadmium sulfide, cadmium selenide, lead sulfide, copper oxide, copperselenide, gallium phosphide, mercury sulfide, mercury selenide,zirconium oxide, zinc oxide, zinc sulfide, zinc selenide, zinc silicate,titanium sulfide, titanium oxide, and tin oxide.
 13. The device of claim11, wherein the nano-phosphors comprise at least one of a rare-earthdoped metal oxide including Y₂O₃:Tb, Y₂O₃:Eu³⁺, Lu₂O₃:Eu³⁺, CaTiO₃:Pr³⁺,CaO:Er³⁺, and (GdZn)O:Eu³⁺, a rare-earth doped yttrium aluminum garnet(YAG) including YAG:Ce³⁺, a rare-earth doped zirconium oxide includingZrO₂:Sm³⁺ and ZrO₂:Er³⁺, rare earth doped vanadates and phosphatesincluding (YVO₄:Eu) and (La,Ce,Tb)PO₄, doped materials having a hostmatrix including one Gd₂O₃, GdO₂S, PbO, ZnO, ZnS, and ZnSe and includingone of a dopant of Eu, Tb, Tm and Mn, and metal-doped forms of zincsulfide and zinc selenide including ZnS:Mn²⁺ and ZnS:Cu⁺.
 14. The deviceof claim 11, wherein the nano-phosphors comprise at least one ofrare-Earth doped YAG, rare-Earth doped ZnS, and rare-Earth doped ZnSe.15. The device of claim 1, wherein the stimulable particles comprise aplurality of color-distinctive light emitters configured to producerespective secondary light emissions from the primary light.
 16. Thedevice of claim 15, wherein the primary light transmitted from the fibermat and the secondary light emissions from the fiber mat produce aresultant white light having a color rendering index greater than 70.17. The device of claim 15, wherein the primary light transmitted fromthe fiber mat and the secondary light emissions from the fiber matproduce a resultant white light having a color rendering index greaterthan
 80. 18. The device of claim 15, wherein the secondary lightemissions from the fiber mat produce a resultant white light having acolor rendering index greater than
 70. 19. The device of claim 15,wherein the secondary light emissions from the fiber mat produce aresultant white light having a color rendering index greater than 80.20. The device of claim 1, wherein the stimulable particles are disposedon surfaces or within a volume of the nanofibers.
 21. The device ofclaim 1, wherein the stimulable particles are entrained in the fibermat.
 22. The device of claim 1, further comprising: a transparentencapsulant encasing the fiber mat.
 23. The device of claim 1, furthercomprising: a light emitting diode configured to produce the primarylight.
 24. The device of claim 23, further comprising: a transparentencapsulant encasing the light emitting diode and the fiber mat.
 25. Thedevice of claim 1, wherein the nanofiber comprise at least one oforganic and inorganic fibers.
 26. The device of claim 1, wherein thenanofibers comprise polymers including at least one of poly(alkylacrylate), poly(methyl methacrylate), poly(ethylene oxide), polystyrene,polysulfone, polylactides, polycarbonate, polyamides, poly(vinylalcohol), derivatives thereof and related polymers, polysilicones,polysulfones, and combinations thereof.
 27. The device of claim 1,wherein the nanofibers include additives to alter at least one of arefractive index and an electrical conductivity of the nanofibers in thefiber mat.
 28. The device of claim 1, wherein the nanofibers comprisetwo groups of fibers.
 29. The device of claim 28, wherein the two groupscomprise fibers having different materials.
 30. The device of claim 28,wherein the two groups comprise fibers having different average fiberdiameters.
 31. A lamp comprising: a primary light source; a fiber matincluding, nanofibers having an average fiber diameter in a rangebetween 100 and 2000 nm, and plural light stimulable particles disposedin association with the nanofibers and configured to produce secondarylight emission upon receiving light from the primary light source at awavelength λ; and said average fiber diameter being comparable in sizeto the wavelength λ in order to provide scattering sites within thefiber mat for the primary light.
 32. The lamp of claim 31, wherein theaverage fiber diameter is in a range between 400 nm to 500 nm.
 33. Thelamp of claim 31, wherein the light emitting diode is configured to emitsaid wavelength λ is in a range between 400 and 500 nanometers.
 34. Thelamp of claim 31, wherein the fiber mat has a thickness in a rangebetween 1 to 500 microns.
 35. The lamp of claim 31, wherein thestimulable particles comprise at least one of quantum dots andnano-phosphors.
 36. The lamp of claim 31, wherein the stimulableparticles comprise a plurality of color-distinctive light emittersconfigured to produce respective secondary light emissions from theprimary light.
 37. The lamp of claim 31, further comprising: atransparent encapsulant encasing the primary light source and the fibermat.
 38. The lamp of claim 31, wherein the primary light source compriseat least one of a light emitting diode, a light emitting diode array, alaser, and a laser diode array.
 39. A method for making luminescentfiber mats, comprising: electrospinning a polymer solution includingstimulable particles; forming from the electrospun solution nanofibershaving a diameter between 100 and 2000 nm and including the stimulableparticles; and collecting the nanofibers to form a fiber mat.
 40. Themethod of claim 39, further comprising: providing a surface coating tothe fiber mat.
 41. A method for making luminescent fiber mats,comprising: electrospinning a polymer solution to form nanofibers havinga diameter between 100 and 2000 nm; coating the nanofibers during theelectrospinning with stimulable particles; and collecting the nanofibersto form a fiber mat.
 42. The method of claim 41, wherein coatingcomprises: introducing the stimulable particles by an electrospray beamdirected to a position removed from an electrospraying tipelectrospinning the polymer solution.
 43. The method of claim 41,wherein the coating comprises: embedding the stimulable particles intothe nanofibers.
 44. The method of claim 41, further comprising:providing a surface coating to the fiber mat.
 45. A method for makingluminescent fiber mats, comprising: electrospinning a polymer solutionto form nanofibers having a diameter between 100 and 2000 nm; collectingthe nanofibers to form a fiber mat; and coating the fiber mat withstimulable particles.
 46. The method of claim 45, wherein the coatingcomprises: immersing the fiber mat in a solvent containing thestimulable particles.
 47. The method of claim 45, further comprising:providing a sonicated solution of the solvent containing the stimulableparticles.
 48. The method of claim 45, further comprising: removing thefiber mat from the solution; and drying the solvent from the fiber mat.49. The method of claim 45, further comprising: providing a surfacecoating to the fiber mat.